SA06270263B1 - Enhancement of Molecular Sieve Performance - Google Patents

Abstract

Enhancement of Molecular Sieve Performance Abstract The present invention relates to a catalyst that converts methanol to light olefins, and the process to manufacture and use this catalyst, are disclosed and protected by the appended claims. The catalyst (SAPO-34) is a useful and useful catalyst of a special quality by preparing it according to this invention. Making the catalyst that has a higher content is used to make the catalyst that has a higher metal content (EL) than what is present in the core of the catalyst. The molecular sieve predominantly has a nearly cuboid crystalline structure with low crack density and better selectivity for light olefins.

Description

Y — _ Enhancement of Molecular Sieve Performance Enhancement of Molecular Sieve Performance Full Description BACKGROUND This invention relates to an enhanced catalyst gy process as a catalyst and its use in the conversion of oxygenates into light olefins and in particular More specifically, the process of the present invention is highly efficient in converting methanol to light olefins

light olefins© due to the use of catalysts being a preferred catalyst. Olefins are traditionally produced from petroleum raw materials by catalytic cracking or steam cracking processes. Cracking (0a) processes, particularly steam cracking, produce light olefin or ethylene Jie light olefins and/or propylene from many types of hydrocarbon raw materials.

alcohols; In particular, the oxygenates A has been scooped for a certain period of time that the oxygenates 0 (light olefins for conversion to light olefin ALE are + methanol “JE” as preferred as methanol and in general; A conversion process of light olefins to methanol is indicated in which Cus (MTO) ') olefins) olefin is converted to - methanol' dec - molecular sieve in the presence of a propylene 5 ethylene molecular sieve.

_Zo has the limited supply of crude oil and the increasing cost of producing it to the need to search for alternative ways and processes to produce hydrocarbon products.

There is an important type of alternative feed material for the production of light olefins represented in oxygenates such as alcohols, specifically ethers s «ethanol 3 methanol such as methyl ethyl » dimethyl ether methyl formate «dimethyl carbonate © dimethyl ethers © ether . These oxygenated materials may be produced by fermentation ¢ or from synthesis gas derived from natural gas 0 or from petroleum liquids or from carbonic materials including coal or recycled plastics; or waste and waste of municipalities and localities; or any other organic material. One of the processes that is particularly useful and useful in the production of olefins is the conversion of methanol into hydrocarbons, particularly into light olefins. The commercial interest in the MTO process is based on the fact that methanol can be obtained from already available raw materials such as coal or natural gas that are processed to produce syngas. Which in turn is processed to produce -methanol The oxygenates are converted into an olefin product through a catalytic process. It is small that the conversion of the feed material containing oxygenates is carried out in the presence of a catalyst for a 0 molecular sieve. Although ZSM-type molecular sieves and other molecular sieves may be used to produce olefins from oxygenates; However, it has been found that "silicoaluminophosphate (SAPO) molecular sieves are of particular value in this catalytic process. Molecular sieves of the type "silicoaluminophosphate (SAPO) are manufactured from silicon 00 sources such as a solution of aluminum « silica sol ; eg aluminum oxide is hydrated yey

_— ¢ — hydrated aluminum oxide and phosphorus such as orthophosphoric acid . in addition to; An organic template or standardizing agent such as tetrathylammonium hydroxide or isopropylamine 0 (di-n-propylamine) is used. The molecular sieve (SAPO-34) belongs to the family of molecular sieves having a zeolitic mineral chabazite (CHA)© structure. The structure of the CHA type molecular sieve with a double hexagonal ring structure is in an aggregate system arranged in the form of an ABC stack when viewed perpendicular to the rhombic axis in the form of regular (pyramidal) triangular prisms. The preparation and properties of the molecular sieve (SAPO-34) are mentioned in many other patents including US Patents Nos. 445011 and COYEATEY 0 and are herein fully incorporated by reference and use. One of the most important models of the conversion process (MTO) is directed to the production of light olefins “that is, olefins containing from (1) to (;) carbon atoms. Accordingly, it is important That a catalyst is used to lead to the production of these products with their maximum productivity 0 and lead to obtaining a high degree of methanol transformation at the beginning of the reaction; nor dhs 1 its effectiveness quickly in the conditions of the process that is exposed to LED and in the transformation process methanol to; the molecular sieve (SAPO-34) shows relatively high product selectivity to both propylene y ethylene ¢ and low product selectivity to We olefin paraffin (4 carbon atoms or more olefin) , e).

N - One of the desirable groups of molecular sieves of the type: 'silicoaluminophosphate' is represented in those groups that have a low silicon content. The silicoaluminophosphate 'molecular sieve' of the type (CHA) structure with low silicon content is particularly desirable for use in the (0410.o) process, and the low silicon content has the effect of reducing However, it has been proven that there is difficulty in manufacturing molecular sieves with a pure phase of “silicoaluminophosphate CHA” with a low ratio of silica to alumina. Several attempts have been made to improve the fabrication or synthesis of molecular sieves of (AIPO4) 0 or (SAPO) One of these methods is to add a fluoride ion source to the synthesis mixture. This method has the disadvantage that many fluorides lead to increased ASH and raise security and environmental concerns due to their toxicity, corrosiveness and volatility. It would be highly desirable to provide a process that avoids their use (the use of these fluorides). US Patent No. 1/17670987 describes the use of vo compounds containing another fluorine These compounds have two or more fluorine-substituteds as a source of the fluoride ion in the synthesis of aluminophosphates or “silicoaluminophosphate” compounds. Although the produced molecular sieves have been described as having the desired 'chabazite' crystal structure, they produce what is JF of the required yield of light olefins when they are used in the process of converting methanol to .olefins yey

Therefore, such compounds are not other fluorine-containing compounds that are the solution that is sought or sought. From GE, it is desirable to find new processes of special quality for the synthesis of molecular sieves that have a structure of the type (CHA), and the urgent need is particularly to find and provide methods for preparing molecular sieves (SAPO) molecular low silica sieves; Which does not need to use hydrogen fluoride or other fluorides. GENERAL DESCRIPTION OF THE INVENTION The present invention provides a method for the synthesis of “molecular sieves” of the “metalloaluminophosphate” type which overcomes many of the problems inherent in prior art 0 methods used for synthesis. molecular sieves of the type “metalloaluminophosphate” provided that YJ prepares a starting crystal of Lal containing from (75) by weight to (770) by weight of metal oxide on the basis that it is a lila oxide Then the formation of a reaction mixture that includes the aforementioned initiating crystals, an aluminum source of 0 ¢, a source of 0 phosphorus, one organic titrant on (JY) and a source of a metal; then inducing and agitating the crystallization process from the reaction mixture in order to form crystals Molecular sieve crystals of the “metalloaluminophosphate” type. The metal source provides a low concentration of metal oxide to the reaction mixture, which is less than the concentration present in the seed of the starting crystal. There are from (1) by weight to (1) £0 (by weight of metal oxide present in a

mentioned reaction mixtures. and in a preferred embodiment of the invention; The metal is silicon and the metal oxide is (D510). This invention also includes the use of these molecular sieves of a type: to form catalysts containing binders to convert 0 methanol into 0 light olefins. In addition to the above, the invention includes a molecular sieve (Juda) of the type : 2 :

"1: AH81110810101005" is a new crystallizer in which the first part of the molecular sieve contains a higher concentration of Le silica than the second part of the molecular sieve. The first part of the molecular sieve contains from (70) to (72 pounds) by weight of silica and includes

0 The second, larger part, which contains the rest of the molecular sieve, contains what ranges from (71) to (75) by weight of silica. Molecular sieves shall be of one type of (CHA) structure, one type of (AED) structure, two endomorphs of both (CHA) and (AED) structure, or a mixture of at least two of the said structures. Detailed description:

10 The process of the invention, Jal, is concerned with the preparation and use of molecular sieves of the type silicoaluminophosphate, which are molecular sieves of the type (ELAPO). Other types of aluminophosphates may also be prepared. Molecular sieves of type (ELAPO) are microporous structure of three-dimensional structure Oe of tetrameric units.

b

ym - surfaces or faces of (POs) (Als) (51.04). In general, compounds (ELAPO) have the following general empirical formula: (ELALP,)O, in which (BL) is a metal chosen from the group consisting of: chromium ¢ manganese ¢ nickel » cobalt » iron ¢ zinc » magnesium 6 silicon ° «¢ and mixtures thereof; “x” is the molar part of (BL) and has a value equal to (° ....) at least; And ty" is the molar part of (AD) and Aad is equal to (a0) over (JY) and "2" is the molar part of (P) and has a value equal to ) 400) on JV so that the sum of .1 = 2 + y + x and when (BL) is 0 mixtures of metals” the “x” is representative of the total amount of the mixture of metals present. (EL) preferred are silicon ¢ and cobalt g 0; magnesium ¢ where silicon is particularly preferred.Molecular sieves of the present invention are fabricated with a seed material that initiates the formation of an al having a higher metal content than that found in the final product of the molecular sieve The said seed material includes a range from (75) to (74 pounds) by weight; preferably an oe range from (TA) to (711) by weight; the most preferred ranges from (700) to (7170) by weight. Any lower level of metal content has been found in other ingredients used in the preparation of the molecular sieve product. Other ingredients mentioned include a range of (71) to (70) by weight in metal; preferably from (EY) (74) by weight in metal.

And - ai! The methods of preparing the various (ELAPO) compounds are well known. As dale molecular sieves (ELAPO) are synthesized by the hydrothermal LAL procedure from a reaction mixture containing reactive sources of “(EL) and ssss ¢ phosphorus; and calibration factor A) calibration template image).

oo The reactive sources of (EL) are metal salts such as nitrate 5 chloride salts. When (EL) is “silicon,” the sources of silicon include forms of silica that are chimney; or colloidal; or precipitated. The sources of aluminum and phosphorus are pseudo-boehmite of phosphoric acids 'alumina' and Jal se titration that is used includes amines and quaternary ammonium compounds.

The 0 calibration agent is tetrathylammonium hydroxide (TEAOH). When the molecular sieves are calcined; it is for each of the vehicles (8170); (SAPO) X-ray diffraction pattern (XRP) identical to the diffraction pattern of the (118©) structure; And it has a high degree of purity in the forms of its types of structure. The crystals at the start of crystallization have a high concentration of silicon higher than the required molecular sieve used to produce crystals of the (CHA) structure type and without

ve used La eas crystals with a silicon concentration higher than the concentration of part Ea of the reaction mixture; the internal growth content will be higher. The reaction mixture consisting of an aluminum source ¢ and a phosphorus source is placed; one or more calibration factors; and crystals crystals start lal; compounds containing one or more metals; in an airtight, leak-proof pressure cooker; Optionally, it is possible

Y. Lined with 0 polytetrafluoroethylene (Jie) plastic and preferably heated under pressure

vey

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self and at a temperature of (p01) to (0 75°C); It is preferred from (100 m) to (70 m) for a period of time sufficient to produce crystals in a typical manner; The time period varies from (1) to (171) hours, preferably from (YE) to (£A) hours. The desired product is recovered by performing a suitable separation method such as centrifugal force. or

.decanting or clarification » filtration Filtration Procedure 0 Molecular sieves of the present invention may be combined with one or more formulation agents; or to form a catalyst composition from a molecular sieve to form a catalyst composition from a molecular sieve It was formulated. The formulation agents may be one or more of the materials or catalytically active materials 1 binding agents selected from the group consisting of binding agents and mixtures of such materials. And ¢ matrix or filler materials sa is done. The formation and shaping of such a composition of the formulated molecular sieve catalyst into a particular by using technical methods of sized particles of useful shape and grain size or forming in “spray drying” or techniques known in such field such as spray drying and in a typical way; Extrusion or by pelletizing the form of granules or small pellets, the interfacial material is effective in reducing the costs of the entire crystallization. This is done by acting 16 in the form of heat sinks that help in retaining heat from the catalyst composition, for example: generation (regeneration); increase the density of the catalyst composition; In increasing the resistance of the catalyst (such as sale) while making the catalyst resist cracking, fragmentation or crushing; in increasing its resistance to wear and corrosion; Also working on

Controlling the rate of transformation in a specific process. yey

11- When the molecular sieve and tissue material (cid) and optionally the binder are combined in a liquid to form a thin slurry solution; There is a need for a mixing procedure, and it is preferable that this mixing be intense and violent.” This is in order to obtain a homogeneous mixture mainly containing sieve oad. Examples of suitable fluids are; Both aldehydes « ketones ¢ alcohol celal « esters © and formations of such liquids. The most preferred liquid is water. The slurry may of the homogeneous mixture may be a colloid-0 solution of sufficient time to produce the desired slurry texture; by approximate particle size and/or by approximate particle size distribution. The molecular sieve, interfacial material and optional binder may be placed and mixed in the same or different fluids; They may all unite in any degree or in any proportion; Whether this is done all at once or in succession” or in the form of a union of a variety or a combination thereof. and in the preferred form; (same cial) and preferably water. The molecular sieve, interfabric and optional binder are combined in a liquid as solids; in dried form or mainly in dried form; or in the form of thin vo slurry solutions, whether done all together or separately. if all solids are added re in the form of mainly dry or desiccant; It is preferable that the addition be made in the form of a fixed and/or controlled amount of the liquid used. in one of the models; The slurry may of the molecular sieve is mixed; binder; and interfacial texture materials or are all ground together to achieve a solution of a homogeneous and uniform slurry mixture of vy. small granules; It is the mixture that is forced into the forming unit to produce the yey sieve catalyst composition

- 1 » Molecular. And mostly; A spray dryer is used as a forming unit. stereotypically; The temperature is maintained sufficient to remove most of the liquid from the slurry mixture and from the resulting molecular sieve catalyst composition. The resulting catalyst composition, when formed in this way, takes the form of micro-spheres

m in general; The particle size of the powder is controlled to some extent by the solids content of the slurry mixture solution. On ln A it is also possible to control both the particle size of the catalyst composition and its characteristic spherical properties by varying the feed material properties of the slurry mixture and the winnowing conditions. It is also; Although winnowing dryers produce and distribute a wide range of particle sizes; It is usual then that compilations are used

(grading liquid) for separating fine particles which may then be ground to a very fine-grained powder; Then it is recycled into the spray dryer feed mixture. After the molecular sieve catalyst composition is formed in a basically dry or dehydrated state; It is usual for heat treatment such as roasting to be performed at elevated temperatures in order to harden and/or activate the catalyst composition thus formed. The traditional environment suitable for roasting is the air

0 which typically contains a small amount of water vapor. Typical roasting temperatures are within a range from (400°C) to 0001 fp (and preferably from (00°C) to

Ave) m); most preferred from (001 M) to oo Vor) and the roasting environment is le | as helium nitrogen; flue gas (a combustion product lacking oxygen); or any variety or combination of such gases. Z Yeuy

In one embodiment the roasting of the formulated molecular sieve catalyst composition is performed in any number of well-known means or apparatus including rotary roasters; fluid bed roasters; Batch production furnaces cand gl and the like. stereotypically; The time required for the calcination procedure depends on the required degree of hardening of the molecular sieve catalyst composition and also on the temperature. in one of the models; The molecular sieve catalyst composition is heated in an atmosphere of i200 As mitrogen at a temperature of (a Ve) (ep Tre) and the heating is performed for a period of time typically ranging from (1) min to dela (Yo) and from Preferred from (1) hour to (10) hours; preferably more than (1) hour to (0) hours; most preferred from (Y) hour to (£) hour. In addition to the molecular sieve of the present invention, the catalyst compositions of the present invention may include one or more of several other catalytically active substances. Hydrocracking Isomerization + polymerization Reformation Hydrogenation Dehydrogenation Dewaxing Hydrodewaxing Absorption Alkylation Transfer groups Alkyl transalkylation and removal of the dealkylation and yey alkyl groups

Hydrodecyclization, oxidation change, soligomerization, oligomerization, disproportionation, reduction

gon ask dehydrocyclization and formations or combinations of such processes.

The catalyst prepared according to the invention is particularly useful in a process intended for converting a raw material comprising one or more oxygen compounds into olefins and one or more 0 olefins and preferably ». ; that the oxygenate compound present in the raw material comprises one or more alcohols, preferably a fatty alcohol (or fatty alcohols); Where Led is the alcohol moiety of alcohol

' carbon atom; It is preferred (Y.) to 1) (for alcohols) with a number of carbon atoms ranging from Yo to (8) carbon atoms. It is (1) carbon atoms; and the most preferred is (01) to (1) of useful as a raw material in the process of the invention comprising straight or branched 25 low-chain fatty alcohols and their corresponding analogues. , ethanol, n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl \o ether, di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid,

and mixtures thereof. In the most preferred embodiment, the raw material is selected from one or more compounds

Of the following compounds: ethanol sl « methanol ¢ i.e. dimethyl ether of « dimethyl ether » or yey

Vo - - from finished formations or combinations, and it is more preferable to “dimethyl ether” methanol (ye), and it is more preferable to be selected from 0 methanol, and it is preferable to convert the raw material comprising one or more oxygen compounds from the materials oxygenates and in the presence of a molecular sieve catalyst composition to an olefin of one or more olefins having from (Y) to (1) carbon atoms; preferably from (1) to (4) carbon atoms. It is more preferable to convert olefins (single olefins) or combinations thereof from a raw feed containing oxygenating substances; Preferably alcohol; and the most preferred methanol » to the preferred olefin (preferred olefins) ethylene and/or propylene. 0 and in general; The process for converting methanol to olefins is referred to as Process 0410. In the MTO process an oxygenated feedstock containing methanol as a principal component of the feedstock and in the presence of a molecular sieve catalyst composition is converted to olefin One or more olefins ¢ and predominantly to where ethylene and/or propylene » Cua is obtained These olefins are often referred to as light olefins (150 light olefins). The amount of light olefins) is based on the fact that the total total weight of the produced hydrocarbon is in the ratio of (700) by weight to “JY” and it is preferable that it be in a ratio of more than (710) by weight. be more (770) by weight.A higher product yield may be obtained through improvements in the operational process of the process as is known in such art.

- 111- The raw feed material may contain one or more diluents; It is typically used to reduce the concentration of the feedstock that is reactive to the sieve catalyst composition; Carbon monoxide, nitrogen + argon, molecular helium. Examples of diluents include

Jie is non-reactive (particularly alkanes paraffins and mainly cele carbon dioxide;); mainly unreactive aromatic compounds; mixtures of propane ¢ ethane « methane ; Preferably nitrogen celal such materials. The preferred diluent is water. Water can be used either in liquid form; or in vapor form; or in that the diluent is added directly to the raw feed material Udy as a combination thereof. or that it is added directly to the reactor; Or to be added to the inner celia to the molecular sieve catalyst formula. In general; The diluent present in feed 0 raw material is within a range ranging from about (70) mol to (750) mol on the basis that it is a percentage and it is preferable that it be in dial of the total number of moles of the raw feed material and the raw material Range limits ranging from (75) mol to (0£) mol. They are of fie hybrid reactors. Reaction processes can take place in various catalytic reactors. Reaction zones with a dense substrate or a fixed substrate and/or with Fluidized bed reaction zones yo or circulating fluidized reactors; upright or upright reactors; and the like fast dae are coupled with. Generation, regeneration and product recovery system. ¢ Reactor system Rapid on reactor system

- 117 -

A fluid bed reactor system shall have a first reaction zone within one or more riser reactors and a second reaction zone within at least one separator vessel; It is preferable that a cyclone comprise one or more cyclones. The riser reactors and breakaway vessel are contained within a single reactor vessel. The freshly prepared feedstock is forced into one or more of the upright or riser reactors into which the molecular sieve catalyst composition or coke treated tissue is introduced. In one embodiment, the molecular sieve catalyst composition or an A-coaled version thereof is brought into contact with a liquid or a gas or a combination thereof prior to being introduced into the riser reactor(s); the liquid is preferably water or methanol 0, and that the gas is an inert gas (nitrogen Jie) if generation or regeneration is required (sale) then the molecular sieve catalyst of the type silicoaluminophosphate can be introduced continuously as a moving bottom layer to the regeneration zone It can then be regenerated and regenerated, for example, by removing carbonaceous materials by oxidation in an oxygen-containing atmosphere In the preferred practice cpl iad the catalyst will be subject to a regeneration and regeneration step by burning the carbonaceous deposits accumulated during

conduct interactions. in the process of converting methanol to olefins using the catalyst compositions of the invention; It is preferable that the process be carried out in the vapor phase, so that contact of the feedstock material is made in the vapor phase in a reaction zone with a molecular sieve = (0) type silicoaluminophosphate' "and under conditions Efficient process like that for example yey

- A, that is, in effective conditions in terms of effective temperature; “light olefins” to produce light olefins and effective pressure; A vacuum velocity by weight per hour (17151) is also effective. Optionally in an effective quantity and by an alternative method; 0 light olefins of the cross-linked diluent to produce light olefins may be carried out in the liquid phase process. when the process is performed in the liquid phase; It is necessary for the process to include a procedure for separating the products formed in liquid reaction media and it can lead to different transformations and different selectivity of the raw feed material in terms of obtaining the light compared to those that are formed olefins on the product with regard to the proportions Relative 0 vapor phase products By the vapor phase process the temperatures that may be used in the process may vary over a wide range; This is what was chosen. 'silicoaluminophosphate' depends at least in part on the catalyst of 0 (Ye) and in general; the process can be carried out at an effective temperature ranging from, and most preferably, to range from fp Ver) m), and preferably from (750 °C) to Ver), and temperatures that are outside the range of degrees (pon) °C to 700 mentioned above are also not excluded from the scope of this invention. Therefore, in general, at the lower end of the temperature range, the lower rate of reaction, the required light yo, is significantly slower. Beyond that, the process may not generate a typical or ideal amount of light olefins. Regardless of these factors, the reaction will still be the required olefins to convert the feed material properly. at least partial to where the Mia products (Vo) take place and at temperatures outside a range from (10100°C) to #0 yey

14- The process is carried out effectively over a wide range of pressures, including intrinsic pressures. And at pressures ranging from (vor) atmospheric pressure to (0001) atmospheric pressure, it is not necessary for light olefins to form at all these pressures. The preferred pressure is Lad between (0000) pressure atmospheric; (001) atmospheric pressure. The pressures referred to here are in favor of the process m except for the inert diluent; and if any of them are present, then they refer to the partial pressure of the raw feed material since it is related to methanol. Also, the pressures that are Outside the range of stresses foreseen and mentioned before are also not excluded from the scope of this invention, though they do not fall within the scope of certain desirable embodiments of the invention. 0 upper pressure range but the process will not be perfect.The process can be carried on for a period of time sufficient to produce the required light olefins.In general, the residence time used to produce the desired product can vary from several seconds to several hours.It will be Already with the knowledge of the practitioner, who is skilled and experienced in such an art, the realization that the residence time can be limited to a certain important extent; by temperature; Sieve 0 _ molecular sieve of the “silicoaluminophosphate” type chosen; the weight-per-hour vacuum velocity (WHSV) and phase (liquid/vapor) selected; possibly by the characteristics of the reactor design chosen. The process is performed over a wide range of (WHSV) feedstock; which is generally within the range of (0.01) hour” to Tel (001) and preferably; within the range of (0.01) 0+) to (£4) an hour. Values greater than (001) yey may be used.

.0 - Cael This is meant to be covered by the current process; Although this is not recommended. It is more Sas that the current process is conducted under process conditions that include a temperature ranging from (pen) to (000 “fp) and a pressure ranging from (00 +) atmospheric pressure to (1001) atmospheric pressure and using (WHSV) is expressed by (1-hour) for each component of the feedstock and has a value ranging from (40) to (0£)-1 hour. Both temperature and pressure are selected (171157) So that the process conditions are effective, i.e. the effective temperature and effective pressure (WHSV) are used; LS, they are combined and in the case of dan coupling, i.e. all of them are linked by mutual correlations; with the molecular sieve of the type : silicoaluminophosphate “0 that has been selected” and with the raw feed that has been selected so that 0 light olefins are produced, and dus is the newly prepared raw feed that is pushed separately or jointly with the vapor of a material Raw feed to the reactor system within a range ranging from (7001) wt. to (Zhe) by wt., preferably from (71) wt. 10) By weight, on the basis that it is a percentage by weight of the total weight of the feed raw material, including any diluent it may contain. It is preferred; that the liquid and steam feed raw materials have the same composition; Or they contain variable proportions of the same or different feedstock and with the same diluent or with a different diluent.

ty - - the molecular sieves of the present invention are of approximately cuboid crystal shape or of approximately cuboid-shaped internally growing al shapes; Or be of a mixture of such forms. This includes crystals, which are cubic in shape; which all dimensions are equal; But this is where the aspect ratio Lad is less than or equal to 0 (*) + preferably less than or equal to (Y) . It is also necessary that the average minimum dimension of the crystal be at least (04) nm; preferably at least (100) nm. As described in the examples; the shape of the crystals and the average minimum dimension of the crystal are determined by checking the sieve Molecular ELAPO and testing it by scanning and examining 0 using a scanning electron microscope (SEM), then measuring and quantifying the crystals in order to obtain an average value for the smallest dimension, without wanting to be associated or bound by any particular theory. From theory, it appears that the minimum thickness is what is required for the diffusion path of propylene 5 ethylene adsorption to be long enough to allow differentiation between the molecules of these two compounds. Most of the "silicoaluminophosphates" that are synthesized using the previously described process usually contain some organic titrants in their pores. For BLAPO compounds to be effective catalysts, they must be Removing the titrant present in the pores by heating the (ELAPO) powder in an atmosphere containing oxygen at a temperature ranging from (100°C).

yy ~ - to 4 (Ver) until the titrant is removed; this process normally takes about a few hours. The embodiment of the invention is one in which the metal content (BL) varies by (0000+) mol to (100+) mol. A particularly preferred model is the 0 model in which the metal (EL) is silicon (usually abbreviated as “SAPO” The SAPO compounds used in the present invention may be any of the compounds described in US Patent No. No. 445457891; the structure (SAPO-34), i.e. the structure A of type (34), is the preferred structure. The structure (SAPO-34) 0 is a silica material - #publication _ with the structure of the chabazite structure 5) Zeolitic CHA The structure is ake-shaped (regular hexagonal prisms) and can be described as a stack of thin layers or flakes stacked along the <001> directions in the alpha structure. The flakes contain On six oblique double loops. and in consecutive chips; All six double Ale loops are in the same direction giving a chain to stack in (AAAA)ve along the <001> directions of said allll. If the direction of inclination is reversed or reversed for each second level, then this G13 is a series of piles in the form of (ABABAB) and this results in a mound of the structure (4100-18). Both of these types of structures consist of the same laminate structure; Stack and stack in a series of different stacks; Whether in the form of AAAA(CHA) or in the form of ABAB(AED). This BLA is the basis for the defect representing a mixture of agglomeration © and stacking chains that are intermediate between these two end members. yey

a Much of the SAPO-34 material exhibits some degree of pronounced cracking which is inferred and evidenced by the widening of the X-ray diffraction peaks and the lateral scratches or notches of the reflections of the electron diffraction patterns. by changing das al and in a particularly specific way the composition (Si JAP) and over wide ranges; The degree of cracking can be affected; where there is a certain tendency that materials with higher (Sif AMP) composition show less cracking; All other manufacturing or synthesis factors are the same. This can be found for many, many different formulations. any way; The degree of cracking is quite sensitive to a number of factors and it is possible to expect exceptions with regard to the tendency of the different synthesis processes within the limits of a narrow and limited range of 0 (for Talha). Variable compositions can also affect the shape of Aged and as an ale it is for For (SAPO-34) preparations that are greater than (75) by weight (58:0) in the final product, the shape has been roughly described as semi-cubic, but most, but not all, of the materials produced are of content within a range of less than (74) by weight (8102) 1 in the final product; The shape and the degree of cracking are inter-correlated.The cracks break ABLE rhombic shapes with regular hexagonal prisms by distinguishing one of the planes equivalent in some way to the <100> levels;crystals grow faster in the directions they It has not cracked; the ©-which take on a plate-like shape tends to produce and form.

P0 - It was found that the selectivity of the conversion reaction to olefins has (7) carbon atoms (©); (7) A carbon atom (C3) in the MTO reaction process is negatively affected by large crack densities (as determined by 7"-ray diffraction of calcined SAPO-34 compounds). In addition to the foregoing, it has been found that more than one dimensional ABE is either cubic in shape or consists of 0e intersecting plates (with cracks along distinct planes) <001> and is useful for selectivity in the direction of the reaction of (0410). These factors show The high ratio of SI/(AHP) would be desirable in (34) SAPO for use in the (MTO) process and in an inappropriate way, it was found that increasing the level of silica leads to raising the acidity of the catalyst, which Jad has reduced the sensitivity of the catalyst to its deactivation by coking.aid A method has now been discovered to produce the SAPO-34 catalyst in the desired form.This method standardizes the reduction of cracking density (AED) without Increasing the level of the whole silica completely.It also increases the degree of growth of the crystal_shape which takes approximately cuboid shape when compared to the plate-like growth is less desirable than allowing the shape of the crystals because Vo is affected without an increase in the level of silicon. In the crystal (0-34 p5). The main principle of the method of preparing the molecular sieves of the invention Jad is to use ed crystals of crystallinity that have a relatively high SI/(AHP) level of 0. The high level of silicon present in the crystals leads to Jal starts until the (SAPO-34) crystals are relatively free to crack. And without wanting to be associated or bound by any particular theory, yey

— m y mm 3

of theories according to ADU that are included; The use of crystals starting to crystallize in the manufacture or synthesis of (SAPO-34) leads to obtaining (SAPO-34) with a lower crack density than

# 2 lbs down from those obtained without the use of erystals crystals starting to crystallize. and take

= . a themselves cubic shape and represent surfaces for nucleation on the metamorphic surface al cas crystals crystals dimensions when ADE leads to obtaining the following Lao shape in all three directions; all 0 8 £ starting crystallization used in crystals in simple cubes. It is preferable to contain le laa crystals and it is preferable (S02) 0m of the present invention to range from (75) by weight to (077) by weight, and it is more preferable to contain (Si0y) by weight A \ ° ) wt to (ZA) ranges from ¢ ssl wt to (© (4) wt (5:0). The following table shows that when (ZY () ranges from . : § then The use of 585 starting crystals containing less than 77 by weight (and 510) 01 when the required and desirable 0 AV was used was propylene ethylene selectivity producing 2 within the desired and desirable range; it was Selectivity (SIO) LS starting crystals (Ae) crystals (Ae) number of silicon dioxide (7) ethylene by weight (0:9) | selective crystal quantity 70) free tractable (S105) (7) propylenes| ex crystals free volatilization 1 crystallization in form by weight of volatilization [crystals of initiating crystals (7) by weight of dry product

aka ta > ana la a sv [oe a a a oe a ee a l

For - _ __ ا ا ______ b_ ell _ ssss —-

yey

L " - The increase in the yield of this quantity is of high importance in improving the efficiency and productivity of the manufacturing unit (070). Package No. (1) is a prior art material without the use of ed crystals with a level higher than (5): 0)”, while the samples from No. (7) to No. (?) are samples that fall within the scope of the present invention and have been prepared according to the method described in the following JE.

Je and then manufacture a quantity of catalyst prepared according to the present invention. and in a pot; (VEO) g of orthophosphoric acid (£A®) ¢ solution was placed and then combined with (£107) g of water. Then to this mixture” (01) g of silica suspension [ Produced by: LS, Aldrich Chemicals “0 #MVIA”] 178 g of (Ive) Sl solution by weight of (TEAOH) tetrathylammonium hydroxide, then (717) g alumina was added as Boehmite’s photo. pseudo-boehmite (sold by “UOP LLC” as “Versal 250” with the addition of (VA) cole g of crystals Js starting type: (SAPO-34) containing (79) by weight silica, then mixing and blending of the previous components was carried out. In addition to that, a quantity of catalyst was manufactured without the high-crystallization silica crystals that were used in the present invention. For comparison purposes, the obtained mixtures were then placed in a Jolin press made of stainless steel equipped with a turbine stirrer, then the mixtures were stirred and then heated to a temperature of (100°C) over a period of time (1) hours, then the temperature was fixed at (100°C) for (4) hours, then heated to a temperature of (175°C) for (0) hours; Then the temperature was kept at a temperature of (175 °C) for (4;) hours. In the end; The mixture was cooled

d - React slowly to room temperature over a period of time (A) hours. Then the solid product was recovered by centrifugal force for (Yo) minutes; Then it was washed with water. This was followed by a series of three additional steps consisting of reconstitution of a thin slurry mixture solution; exposure to centrifugal force; promotion; Then m of the product was dried overnight at a temperature of (90 L)x. Several differentiation methods were used to examine and test the distinctive properties of the obtained product, including crack intensity (X-ray diffraction =) and shape (using transmission electron microscopy and using scanning electron microscope); Of the (CHA) structure type and only small amounts of (ART) cracking, sample No. (1) showed a broadening of some peaks and the emergence of new peaks in the diffraction pattern, which indicates the presence of significant amounts of Fracture of the (AED) Further data analysis confirmed these conclusions. Scanning electron microscopy showed that the shape of both samples (); vo (©) is coherent with cubes; or thick Or internally growing plates, while the shape of the sample was best described on Led in the form of very thin plates (plates).Transmission microscope confirmed this comparison of the shape of the samples. Additional analysis of the samples revealed that there are mostly areas with “adi ya silicon” content, and that is typical in the center of the grains, which were explained and explained (Yo) in an acceptable way in the form of granules for the crystals of EN starting. Materials at the edges of the grains tend to contain lower levels of silicon yey.

Claims (1)

Either - elements of protection 11- The hydrocarbon conversion process includes: Y { Introducing a feedstock into the reactor system in the presence of a 7 molecular sieve of the metallo-aluminophosphate type prepared first by providing cf a reaction mixture that includes an amount of 05015 crystals starting to crystallize: metallo-aluminophosphate containing 8 © to ZY. by weight metal oxide on a dry oxide basis; phosphorus Aas ¢ aluminum ¢ source of at least one organic form” and a metal source; It stimulated the formation of crystals sieve A molecular sieve of the aforementioned metallo-aluminophosphate type from mixture 4 of the reaction where metal oxide is present with an agglomeration concentration of less than about 779 by weight; And chapter 01 molecular sieve, Jie! metallo-aluminophosphate 11 mentioned; VY b) draw an inrush current out of the reactor system; and OY c) pass the outflow stream through the recovery system and extract VE at least one conversion product. 1 7 - The process according to claim (1), where the feedstock includes one or more Y-oxygenates. oxygenates the process according to claim (1); where the oxygenate - ¥ 1 or mixtures thereof comprise one or more dimethyl ether » methanols containing Y yey 1 + - the operation under claim (1); where one or more transformation products include Y on one or more light olefins. 1 > - process under claim o£) wherein one or more light olefins comprise on propylene « ethylene and mixtures thereof. 1 + - hydrocarbon conversion process according to Paul Protection 810; Mentioned is metal oxide, where it is (1) X (1) According to the claim, hydrocarbon conversion - 1 1 metallo-aluminophosphate molecular sieve where the molecular sieve is Y SAY An almost rectangular crystalline outgrowth or intergrowth of outgrowths ; Almost parallel surfaces, or a mixture thereof. A 1 - Lids hydrocarbon conversion process of the claimant OY (1); where the organic form includes at least one form selected from 1 set consisting of: tetraethyl ammonium hydroxide (TEAOH), tetraethyl ammonium phosphate, t tetraethyl ammonium fluoride, tetraethyl ammonium bromide, tetraethyl © ammonium chloride, tetraethyl ammonium acetate, dipropylainine (DPA), 1 isopropylamine, cyclohexylamine, morpholine, methylbutylamine, morpholine, v diethanolamine, and triethylamine. A Als (1) According to the hydrocarbon conversion claim, the hydrocarbon conversion process - 4 1 metallo-aluminophosphate of the molecular sieve type, where the molecular sieve CHA 7 has frameworks of internally growing types of AFT, a framework of the type “ CHA is a Y frame; - Wah or a mixture of at least two of the mentioned tire types 1 0 - hydrocarbon conversion process according to claim Y (); It also includes the step of calcining the crystalline molecular sieve to obtain 1 molecular sieve of -metallo-aluminophosphate type. 11.1 The hydrocarbon conversion process of claim 0 Y + also includes a formation step of Jaa comprising crystallized metallo-aluminophosphate ¥ using at least one forming agent. 1 1 - The process of converting the hydrocarbon according to claim (10), since the aforementioned reaction mixture, with the exception of the aforementioned metallo-aluminophosphate crystals, includes - about 1 to Ze by weight 0 511168 1” 1 - The hydrocarbon conversion process according to the claim Cua (ve) OY that the aforementioned reaction mixture excluding the crystals of ? | The mentioned metallo-aluminophosphate contains about (JY 4 7 by weight) silica yey 1 4 - The hydrocarbon conversion process according to the protection element (Y) \) + as the aforementioned crystals contain about A to Jo by weight metal oxide 1. yey